Stable carbon and nitrogen isotopic compositions of tropical ...

SERIES B CHEMICAL AND PHYSICAL METEOROLOGY PUBLISHED BY THE INTERNATIONAL METEOROLOGICAL INSTITUTE IN STOCKHOLM

Stable carbon and nitrogen isotopic compositions of tropical atmospheric aerosols: sources and contribution from burning of C3 and C4 plants to organic aerosols By S TE L Y U S L . M K O M A 1 , 2 * , K I M I T A K A K A W A M U R A 1 , ER I T A C H I B A N A 1 a n d P I N G Q I N G F U 1 , 3 , 1Institute of Low Temperature Science, Hokkaido University, N19 W08, Kita-ku, Sapporo 060-0819, Japan; 2Faculty of Science, Department of Physical Sciences, Sokoine University of Agriculture, P.O. Box 3038, Chuo Kikuu, Morogoro, Tanzania; 3LAPC, Institute of Atmospheric Physics, Chinese Academy of Science, Beijing 100029, China (Manuscript received 27 November 2012; in final form 29 November 2013)

ABSTRACT In this paper, we report for the first time the d13C and d15N data for PM2.5 and PM10 aerosols collected in Tanzania during MayAugust 2011 together with total carbon (TC) and nitrogen (TN) contents. Mean TC concentrations were 6.592.1 mg m 3 in PM2.5 and 9.293.5 mg m 3 in PM10. d13C of TC ranged from 26.1 to 20.6 with a mean of 23.6 in PM2.5 and from 24.4 to 22.4 with a mean of 23.6 in PM10. We found substantially greater d13C values in PM2.5 samples during dry season as well as strong positive correlation between levoglucosan (and nss-K) and TC in PM2.5. These results suggest a significant contribution from burning of C4 plants to fine organic aerosol formation. TN contents showed a mean of 0.790.3 mg m 3 in PM2.5 and 0.890.2 mg m 3 in PM10. d15N ranged from 13.4 to 22.1 with a mean of 16.292.7 in PM2.5 and 10.4 to 18.7 with a mean of 13.792.2 in PM10. d15N showed higher ratios in fine particles than coarse particles in both wet and dry season. The relatively high d15N values suggest isotopic enrichment of 15N in aerosols via exchange reaction between NH3 (gas) and NHþ 4 (particle). We found 2 2 2 a strong correlation between TN and NHþ 4 (r 0.94 in PM2.5 and r 0.86 in PM10) and NO3 (r 0.48 in 2 PM2.5 and r 0.55 in PM10). We also found that organic nitrogen is less significant than inorganic nitrogen in the Morogoro aerosols. Based on stable carbon isotopic composition, contributions of burning C3 plants to TC were estimated to range from 42 to 74% in PM2.5 and from 39 to 64% in PM10, whereas those of C4 ranged from 26 to 58% in PM2.5 and from 36 to 61% in PM10. These results suggest that burning activities of C3 and C4 plants contribute to organic aerosol formation in Tanzania. Keywords: PM2.5 and PM10, aerosols, isotopic composition of total carbon and nitrogen, C3 and C4 plants, Tanzania

1. Introduction Stable carbon (d13C) and nitrogen (d15N) isotopic compositions can provide complementary information about sources of aerosols and have long been applied in various environments (Turekian et al., 1998; Lajtha and Marshall, 1999; Narukawa et al., 2008; Pavuluri et al., 2010). Also, d13C and d15N of bulk aerosols have been used to better understand the contributions of various sources to organic aerosols including biomass and biofuel burning (Ballentine

*Corresponding author. email: [email protected]

et al., 1998; Martinelli et al., 2002; Widory, 2007). In tropical sites, biomass burning is widespread as it serves to convert forests to agricultural and pastoral lands. The field burning of agricultural waste and fuel wood burning are known to produce aerosol particles and trace gases that play important roles in atmospheric chemistry and climate changes (Levine et al., 1995). Although studies on stable carbon and nitrogen isotope ratios of aerosols have been reported from several sites, little is known in Africa and no extensive studies have been conducted on d13C and d15N simultaneously (Billmarka et al., 2005; Rommerskirchen et al., 2006; Vogts et al., 2009). Further, the relation of nitrate and ammonium ions

Tellus B 2014. # 2014 S. L. Mkoma et al. This is an Open Access article distributed under the terms of the Creative Commons CC-BY 4.0 License (http:// creativecommons.org/licenses/by/4.0/), allowing third parties to copy and redistribute the material in any medium or format and to remix, transform, and build upon the material for any purpose, even commercially, provided the original work is properly cited and states its license. Citation: Tellus B 2014, 66, 20176, http://dx.doi.org/10.3402/tellusb.v66.20176

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S. L. MKOMA ET AL.

to total aerosol nitrogen has not been studied in Africa, although they could provide additional information on the source types of aerosols (e.g., Kundu et al., 2010a; Pavuluri et al., 2010). In this paper, we present the measurement results on stable carbon and nitrogen isotopic composition in the ambient aerosols collected at a rural background site in Tanzania during an intensive field campaign carried out in May through August 2011. Here, we report the concentrations of total carbon (TC) and total nitrogen (TN) and their isotopic composition to better understand their potential sources. Southern African savanna where Tanzania locates is an important source region of biomass burning and long-range atmospheric transport of aerosols on a local and global scale (Lajtha and Marshall, 1994). This study provides for the first time baseline data sets of stable C and N isotopic composition of atmospheric aerosols from Tanzania, East Africa.

2. Experimental 2.1. Aerosol sampling PM2.5 and PM10 aerosol sampling was carried out at Solomon Mahlangu Campus of Sokoine University of Agriculture in Morogoro (06847?40.8ƒS; 37837?44.5ƒE, altitude 504 m, a.s.l.) from 30 May to 8 August 2011. This typical rural site (300 000 inhabitants) is located at about 200 km west of the coast of the Indian Ocean where the city of Dar es Salaam, a business capital in Tanzania, is located (Fig. 1). Aerosol samples were collected using PM2.5 and PM10 low-volume filter samplers operated in parallel; one of the samplers was equipped with a Rupprecht and

Fig. 1.

Pataschnik PM2.5 inlet and the other with a Gent PM10 inlet (Hopke et al., 1997). Samplers were placed at a meteorological synoptic station on campus, and aerosol collections were made at 2.7 m above ground level. Each sampler used NILU stacked filter unit (SFU) cassettes, in which the front and back quartz fibre filters (Pallflex 2500QAT-UP, 47 mm) were placed in series. The samplers operated at a flow rate of 17 L/minute. The quartz filters were pre-baked at 4508C for 4 hours in a furnace to eliminate adsorbed organics before use. The two quartz fibre filters (front and back) in the PM2.5 inlet and PM10 filter holder were intended to assess the extent of the artefacts. Quartz fibre filters can adsorb volatile organic compounds (VOCs) causing positive artefacts when measuring the PM. On the other hand, semi-volatile organic compounds (SVOCs) in aerosols may partially evaporate during sampling resulting in negative artefacts (Turpin et al., 2000; Hitzenberger et al., 2004). The PM mass and organic species (e.g., TC) determined on the back quartz filters were insignificant and therefore in this study the data from the front filter were adopted. During the campaign, a total of 21 sets of samples and two field blanks for each of the PM2.5 and PM10 samplers were collected on an approximately 24-hour basis and exchange of filters was performed at 7:30 am. Before and after sampling, quartz filters were placed in a pre-heated glass vial with a Teflon-lined screw cap and kept frozen at 208C during storage. The samples were transported to the Institute of Low Temperature Science, Hokkaido University and stored in a freezer at 208C prior to analysis. All procedures were strictly quality-controlled to avoid any possible contamination of the samples.

Map showing the location of the sampling site of Morogoro, Tanzania.

STABLE CARBON AND NITROGEN ISOTOPIC COMPOSITIONS

2.2. Aerosol analysis For the measurements of TC and TN contents and their isotopic compositions, a punch (1.54 cm2) of each quartz filter sample was cut off and used. The filter punch was rounded using a pair of flat tipped tweezers, placed into a tin cup and then caked into a ball. Before use, the tin cup was cleaned with acetone under ultrasonication to remove organic and other contaminants. The samples (filter plus tin cup) were then analysed for TC and TN and their isotopic compositions using elemental analyser (EA; model Carlo Erba NA 1500) and EA/isotope ratio mass spectrometer (IRMS) (Finnigan MAT Delta Plus) (Narukawa et al., 1999; Kawamura et al., 2004). Isotope data reported as d13C and d15N values were defined as: d13 C ð%Þ ¼ 13 C=12 C = 13 C=12 C 1 1000 sample

15

d N ð%Þ ¼

15 N=14 N

sample

3

afternoon. Generally, aerosol sampling was mostly conducted on days with no rain and/or a very weak rain.

2.4. Air mass backward trajectories In order to identify the source regions, backward air mass trajectories at arrival level of 500 m above the ground were computed using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model of the NOAA/ ARL (http://ready.arl.noaa.gov/HYSPLIT.php; Draxler and Rolph, 2012). The isentropic backward 5-d air mass back trajectories for 24-hour samples indicated that the sampling site in Morogoro was mainly influenced by air masses from the Indian Ocean with mixtures of continental origins over Madagascar, through Mozambique and Tanzania (Fig. 2).

standard

= 15 N=14 N

standard

(1) 1 1000 (2)

Before running the real samples for the determination of TC, TN, d13C and d15N ratios, we checked the instrument conditions with an empty tin cup three times and also evaluated a five-point calibration curve using acetanilide standard with the procedural blanks. The replicate analyses were not conducted due to the small size of actual sample filters. The analytical errors for d13C measurement based on repeated analyses of atmospheric aerosol samples at our laboratory were within 0.2 and those for d15N are 0.3 (Kawamura et al., 2004). We confirmed the similar analytical errors by running the authentic standards (acetanilide). TC and TN contents reported here were corrected for the field blanks, whose levels are B1.4% of actual samples. d13C and d15N values were also corrected for the field blanks using an isotopic mass balance equation. Details for the measurement of LG and water-soluble inorganic ions can be found in Mkoma et al. (2013), and a nonparametric correlation test (Spearman test) was applied to our data sets to explain the relationship between variables.

2.3. Meteorology Meteorological parameters including precipitation, ambient temperature and relative humidity were recorded at a meteorological synoptic station at sampling site during sampling days. The prominent wind pattern during the sampling period was characterized by the southeasterly (SE) monsoons with daily average wind speed of 7.8 m s 1. The average ambient temperature was 258C with a range of 22298C. The daily average relative humidity ranged from 65 to 96% in the morning hours and from 41 to 60% in the

3. Results and discussion 3.1. Total aerosol mass, TC, TN, d13C, d15N, and TC/TN and TC/PM ratios The variations of PM2.5 and PM10 aerosol mass concentrations are shown in Fig. 3. Mean aerosol mass concentrations for PM2.5 and associated standard deviation were 33.49 9.7 mg m 3 (range: 16.6-61.3 mg m 3), whereas those of PM10 were 54.2916.1 mg m 3 (range: 35.7-99.5 mg m 3). The aerosol mass concentration levels obtained here are comparable to or lower than the previous studies from Morogoro (Mkoma et al., 2009a, b). The mean PM mass back/ front filter ratios from the quartz fibre filters for the PM2.5 and PM10 during sampling period were determined. On average, 716% of the PM mass on the front filters for the two size fractions was due to sampling artefacts. The artefacts are thought to be mostly positive, i.e., due to adsorption of VOCs and of volatile inorganic species (Turpin et al., 2000; Hitzenberger et al., 2004). In previous 2005 and 2006 campaigns at Morogoro on average 9 to 13% of the PM mass were due to sampling artefacts (Mkoma et al., 2010). Concentrations of TC and TN in PM2.5 and PM10 are presented in Tables 1 and 2, respectively. TC contents ranged from 3.1 to 10.4 mg m 3 (mean: 6.592.1 mg m 3) in PM2.5, whereas those of PM10 were 4.218.0 (mean: 9.293.5 mg m 3). On average, TC accounted for 20.8% (range: 9.6 34.7%) of PM2.5 and 17% (range: 11.828.7%) of PM10 mass. These results show elevated concentrations of TC in months of JulyAugust, suggesting enhanced biomass/ biofuel burning activities and contributions of primary biogenic particles (mostly in PM10 fraction). Domestic use of fuel wood and charcoal, which are common in Tanzania, could also contribute to the observed levels of TC at our sampling site.

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Fig. 2.

S. L. MKOMA ET AL.

Typical examples of 5-day backward air mass trajectories arriving at Morogoro during the MayAugust 2011 sampling period.

higher d13C values in PM2.5 samples, suggesting that biomass burning of C4 plants dominated in savanna grasses occasionally contributes to the formation of organic aerosols in the region (Rommerskirchen et al., 2006). The high range for d13C observed in PM10 may be influenced by soil dust contributions and biogenic emissions of plant waxes. The isotopic mass balance eqs. (3) and (4) were used to calculate the isotope ratios of fine (PM2.5) and coarse (PM10 PM2.5) particles (Kawamura and Watanabe, 2004). d13 Ccoarse ¼ d13 CðPM10 Þ Ffine d13 Cfine =Fcoarse (3) d15 Ncoarse ¼ d15 NðPM10 Þ Ffine d15 Nfine =Fcoarse (4)

The mean percentage of PM10 carbon (or nitrogen) that is actually PM2.5 and which fraction is coarse were calculated for the campaign on the basis of the data for PM2.5 and PM10 samples taken in parallel and then averaged over all samples from the campaign. The mean PM2.5/PM10 carbon ratios were 68919% (range: 34%-98%). The results indicate that most of PM10 carbon was mainly in fine (PM2.5) fraction during the campaign. The possible main contributors to carbon are biomass burning particles and secondary aerosol, both of which are known to be preferentially associated with PM2.5 fraction (Fuzzi et al., 2007). In contrast, a small contribution from soil dust may be associated with coarse particles. d13C of TC ranged from 26.1 to 20.6 in PM2.5 and 24.4 to 22.4 in PM10 with a mean of 23.6 in both fractions (Table 1 and 2). We found substantially

where d13Ccoarse and d15Ncoarse, and d13Cfine and d15Nfine are isotopic composition of (C and N) coarse and fine

120 PM2.5

PM mass (µg m−3)

100

PM10

80 60 40 20

8/8

7/8

6/8

5/8

4/8

3/8

2/8

1/8

29/7

28/7

13/6

12/6

9/6

7/6

6/6

5/6

4/6

2/6

1/6

31/5

30/5

0

Day of May to August 2011 Fig. 3.

Trends of aerosol mass concentrations (mg m 3) in PM2.5 and PM10 during the MayAugust 2011 sampling period at Morogoro.


Table 1. (n21)

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Concentrations of TC and TN (mg m 3), their isotope ratios (), TC/TN and TC/PM (%) in PM2.5 from Morogoro, Tanzania

Date 30/5/2011 31/5/2011 1/6/2011 2/6/2011 4/6/2011 5/6/2011 6/6/2011 7/6/2011 9/6/2011 12/6/2011 13/6/2011 28/7/2011 29/7/2011 1/8/2011 2/8/2011 3/8/2011 4/8/2011 5/8/2011 6/8/2011 7/8/2011 8/8/2011 Mean9SD

d13C

d15N

TC

TN

TC/TN

TC/PM

TN/PM

25.4 25.8 25.1 25.9 24.8 24.3 25.6 25.6 26.1 NA NA 22.6 22.0 21.8 20.6 21.2 NA 22.4 21.3 21.7 21.8 23.691.9

NA 16.1 13.5 NA 13.4 15.3 NA 14.1 NA NA NA 20.3 13.5 22.1 17.2 17.9 NA 14.2 NA 16.4 16.8 16.292.7

6.1 7.2 3.7 6.0 3.9 4.5 7.4 5.3 3.1 4.5 7.9 8.0 10.4 9.7 9.7 8.3 6.6 6.9 4.2 5.5 7.7 6.592.1

BDL 0.5 0.6 BDL 0.4 0.4 BDL 0.4 BDL BDL 0.6 0.9 1.4 0.9 1.5 0.6 0.7 0.7 BDL 0.7 0.6 0.790.3

NA 13.9 6.3 NA 10.4 11.5 NA 12.8 NA NA 13.7 9.2 7.6 11.4 6.3 12.8 10.2 9.6 NA 8.1 13.5 10.592.6

22.4 21.8 12.9 26.4 11.6 17.8 20.3 22.1 19.0 17.5 20.6 21.9 34.7 30.0 23.7 27.3 10.8 14.5 9.6 17.5 20.8 20.896.4

NA 1.6 2.0 NA 1.1 1.6 NA 1.7 NA NA 1.5 2.4 4.6 2.6 3.8 2.1 1.1 1.5 NA 2.2 1.5 2.291.0

BDL: below detection limit, DL: ca. 0.02 mg m 3 for TC and 0.05 mg m 3 for TN. NA: not available.

particles, respectively. Ffine is a fraction of fine particles, whereas Fcoarse is a fraction of coarse particles (FfineFcoarse 1). Table 3 shows the results of isotopic compositions of C and N in the fine and coarse fractions during 2011 wet and dry season samplings. During dry season (28 July to 8 August), fine particles are more enriched with 13C, suggesting more contribution from the burning of C4 plants (they have evolved in the dry conditions in the history of plants) than coarse particles. C4 plants are probably more active when weather is dried in East Africa. However, in the wet season (30 May to 13 June), d13C of coarse particles showed higher ratios than fine particles. Although it is difficult to explain the reason, we consider that there is some unknown process behind the result. TN contents had a narrow range of 0.41.6 mg N m 3 (mean: 0.790.3 mg N m 3) in PM2.5 and 0.61.6 mg N m 3 (mean: 0.890.2 mg N m 3) in PM10. TN comprised of 1.1 4.6% (mean: 2.2%) of PM2.5 and 1.12.6% (mean: 1.6%) of PM10 mass. Variations of TN may be due to the wet scavenging (most N species are water-soluble) and the differences in photochemical atmospheric processes. The calculated mean percentage ratio of PM2.5 to PM10 nitrogen during the campaign was 72914% ranging from 57 to 98%. The ratios indicate that most of nitrogen was mainly present in fine (PM2.5) fraction and possibly associated with

biomass/biofuel burning activities and secondary aerosols. TC/TN weight ratios range from 6.3 to 13.9 in PM2.5 and from 6.9 to 14.1 in PM10 (Table 1 and 2). The higher C/N ratios suggest more contributions of organic aerosols from biomass/biofuel burning in East Africa. A strong positive correlation (r2 0.88, p B0.001) between TC and TN in PM10 (Fig. not shown here) may indicate that TC and TN have a common source. We also found strong correlations (r2 0.70) between PM10 mass and TC (p B0.001) or TN (p B0.05) (Fig. not shown here). d15N of TN in PM2.5 ranged from 13.4 to 22.1 (mean: 16.292.7), whereas those of PM10 are slightly lower ranging from 10.5 to 18.7 (mean: 13.792.2) (Tables 1 and 2). The isotopic compositions of N in the fine and coarse fractions of Morogoro during wet and dry season campaigns are given in Table 3. The d15N showed higher ratios in fine particles than coarse particles in both wet and dry season. These results suggest that enrichment of 15N in fine particles is more important than coarse particles in both seasons. The higher d15N ratios in dry season further indicate that isotopic enrichment of 15N in the aerosols is more significant in dry season due to partitioning reaction between gas (NH3) and particle [(NH4)2SO4] (Pavuluri et al., 2010). d15N variability at our site could also be controlled by biomass burning activities, and by nitrogenous species (e.g., NH3)

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Table 2. (n21)

S. L. MKOMA ET AL.

Concentrations of TC and TN (mg m 3), their isotope ratios (), TC/TN and TC/PM (%) in PM10 from Morogoro, Tanzania

d13C

d15N

TC

TN

TC/TN

TC/PM

TN/PM

24.0 24.1 24.4 24.4 23.4 23.0 23.7 23.9 23.8 23.8 23.4 23.9 23.5 22.7 22.6 22.4 23.9 23.8 23.7 NA 23.4 23.690.5

10.4 11.6 NA NA 13.0 12.9 12.7 13.4 10.7 11.2 15.4 13.4 16.5 17.0 18.7 14.6 NA 12.9 13.9 NA 14.7 13.792.2

6.0 8.2 6.8 8.3 4.2 6.4 9.7 7.5 6.4 9.3 11.4 5.9 10.5 16.0 18.0 12.6 11.7 8.8 5.3 9.8 11.2 9.293.5

0.7 0.7 BDL BDL 0.6 0.7 0.8 0.7 0.7 0.8 1.0 0.6 0.9 1.2 1.6 0.9 BDL 0.8 0.5 0.8 0.8 0.890.2

9.2 11.0 NA NA 6.9 9.3 12.0 10.3 8.7 11.6 11.9 10.2 11.1 13.2 11.4 14.1 NA 11.2 11.5 12.1 14.1 11.191.8

13.3 ND 11.8 16.1 11.8 17.7 20.1 18.2 15.2 16.8 19.9 12.0 28.7 20.3 18.1 21.3 14.6 15.5 12.2 17.8 20.1 17.094.2

1.4 NA NA NA 1.7 1.9 1.7 1.8 1.8 1.4 1.7 1.2 2.6 1.5 1.6 1.5 NA 1.4 1.1 1.5 1.4 1.690.3

Date 30/5/2011 31/5/2011 1/6/2011 2/6/2011 4/6/2011 5/6/2011 6/6/2011 7/6/2011 9/6/2011 12/6/2011 13/6/2011 28/7/2011 29/7/2011 1/8/2011 2/8/2011 3/8/2011 4/8/2011 5/8/2011 6/8/2011 7/8/2011 8/8/2011 Mean9SD

BDL: below detection limit, DL: ca. 0.02 mg m 3 for TC and 0.05 mg m 3 for TN. NA: not available.

0.029, range: 0.0090.042) and PM10 (mean: 0.027, range: 0.0120.039). Figure 5 shows strong positive correlations between TC and LG (p B0.001) in both PM2.5 and PM10 and nss-K (p B0.05 in PM2.5 and p B0.001 in PM10) suggesting an important contribution to TC from biomass/biofuel burning emissions from residential wood burning and charcoal-making operations in East Africa. The nonsea-salt (nss)-K was calculated using Na as a reference tracer for sea-salt and obtained by subtracting the sea-salt contribution from the measured K data sets (Riley and Chester, 1971). The intercepts of the least square fit are all positive on TC axis, implying that in addition to biomass burning there is a contribution to TC either from direct emission of bioaerosols from plants or from secondary formation of organic aerosols from biogenic VOCs.

from agricultural sources, in particular cattle raising (Streets et al., 2003).

3.2. Temporal variations of TC, d13C and relations with biomass burning tracers Temporal variations of TC and its isotope ratio (d13C) for PM2.5 and PM10 are shown in Fig. 4. The highest TC contents were observed between 29 July and 2 August for PM2.5 and 23 August for PM10. The elevated TC concentrations can be associated with the enhanced source strength of local and regional biomass burning activities. In spite of variable concentrations of TC (3.118.0 mg m 3) and LG (0.0380.659 mg m 3, data from Mkoma et al., 2013), LG/TC ratios (on carbon basis) did not show a significant difference between PM2.5 (mean:

Table 3. Isotope ratios () of carbon and nitrogen in the fine and coarse fractions of Morogoro, Tanzania, during 2011 wet and dry season campaigns Wet season 13

Min. Max. Mean9SD

13

Dry season 13

13

Wet season 15

15

Dry season 15

d Cfine

d Ccoarse

d Cfine

d Ccoarse

d Nfine

d Ncoarse

d Nfine

d15Ncoarse

26.1 24.3 25.490.6

23.8 17.8 21.592.1

22.6 20.6 21.790.7

30.8 23.4 26.593.0

13.4 16.1 14.791.2

7.1 12.5 9.192.9

13.5 22.1 17.493.1

5.8 19.7 12.195.1


20

-15 δ13C

TC (μg m−3)

PM2.5 -20

10 -25

5

(b)

0

-30

20

-15 PM10

δ13C

TC

15 TC (μg m−3)

δ13C (‰)

TC 15

-20 10

δ13C (‰)

(a)

7

-25

5 0 8/8

7/8

6/8

5/8

4/8

3/8

2/8

1/8

29/7

28/7

13/6

12/6

9/6

7/6

6/6

5/6

4/6

2/6

1/6

31/5

30/5

-30


Temporal variation of TC and d13C in (a) PM2.5 and (b) PM10 during the MayAugust 2011 sampling period at Morogoro.

The background TC concentrations in PM2.5 and PM10 (Fig. 4) could be involved with emissions from soil dust and biogenic sources (nss-K can be emitted from biogenic debris and soil dust). The weak correlation observed between TC and nss-K in PM2.5 (Fig. 5a) could be associated with secondary organic aerosols (high temperature and most organic compounds are water-soluble). Use of wood and charcoal for domestic cooking and heating is common in Tanzania, which is enhanced in months of March through May. On the other hand, Na/TC ratio in the marine aerosols was reported to be 2.3 (Cavalli et al., 2004) and its relation to d13C of TC is used to understand the relative contribution of seawater organics to marine aerosols (Narukawa et al., 2008). Our average Na/TC ratio was 0.18, and no correlation was found between d13C with Na/TC ratios and even with NO 3 (Fig. not shown). This suggests that the influence of sea-salt particles to our site is less important. The d13C was poorly correlated with TC in PM2.5 2 (r 0.22), but somewhat good correlation was obtained for PM10 (r2 0.37) (Fig. not shown here). The correlation between d13C and TC may indicate possible emissions of soil dust and biological particles and a possible condensation of volatile and semi-volatile organics derived from biomass burning of C4 plants on pre-existing particles.

3.3. Temporal variations in TN, d15N and contributions of N species to TN Figure 6 shows temporal variations of TN and d15N for PM2.5 and PM10. TN contents in PM2.5 show high levels on 29 July and 2 August, whereas the levels in PM10 show a gradual increase during sampling period with highest values on 12 August. On the other hand, d15N showed higher values on 2 August in both fractions. The relationships among biomass burning tracers (nss-K and LG, hereafter abbreviated as LG), TN and d15N were examined (Fig. not shown here). TN showed good correlation with nss-K (r2 0.63, p B0.001 in PM2.5 and r2 0.55, p B0.001 in PM10) and LG (r2 0.33, pB0.05 in PM2.5 and r2 0.42, p B0.001 in PM10). In contrast, d15N showed poor correlation with nss-K (r2 0.33) and LG (r2 0.14) in PM2.5 but showed good correlation with nss-K (r2 0.67, p B0.001) and LG (r2 0.51, p B0.05) in PM10. The NHþ 4 and NO3 , which are important constituents of TN (Pavuluri et al., 2010), may have been enhanced in those days from local sources possibly by gas-to-particle conversion of NH3 and NOx (secondary formation). Variabilities of d15N for both sizes (PM2.5 and PM10) were larger than those of d13C. These variations may be

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Fig. 5.

S. L. MKOMA ET AL.

Relation between TC with levoglucosan and nss-K in PM2.5 (a, b) and PM10 (c, d) during the sampling period.

due to changes in the contribution of local sources and secondary formation pathways of nitrogen aerosols (Widory, 2007; Pavuluri et al., 2010). However, larger d15N values for PM10 in JulyAugust 2011 may have originated from soil dust in addition to the influence of biomass burning activities (Turekian et al., 1998), being supported by good correction (r2 0.62) between d15N and Ca2 (crustal element) for PM10 in same period. It is important to note that our site is neither influenced by fossil fuel combustion products that are less enriched with 15N (d15N B0) (Widory, 2007), nor contributed by particulate nitrogen from marine emissions; d15N did not correlate with Na/TN ratios. Hence, relatively high d15N ratios obtained in the present aerosol samples could not be explained by the influence of marine aerosols and anthropogenic activities. The contributions of inorganicN species (NHþ 4 and NO ) to TN (inorganic plus organicN) measured by 3 EA were calculated. NHþ was found to account on 4 average for 62.5% of TN (range: 20.988.7%) in PM2.5 and 34.4% (range: 7.985.0%) in PM10, whereas NO 3 comprised on average of 4.1% (range: 2.88.8%) and 8.0% (range: 3.517.5%) in PM2.5 and PM10, respectively. Higher contribution of NHþ 4 to TN than NO3 may indicate a strong NH3 emission from biomass burning, cattle (livestock) farms, open sewage and landfills (Sutton et al.,

2000). Outflow of domestic sewage systems and dumping of solid waste into open landfills are common in Tanzania. On the other hand, the global nitrogen contributions from animal manure have been estimated to be between 40 and 60% for NHþ 4 and below 10% for NOx (Oenema and Tamminga, 2005). Figure 7 shows relations between þ NHþ 4 , NO3 , NH4 plus NO3 , and TN in PM2.5 and PM10. Strong positive correlations (p B0.001 in PM2.5 and p B0.05 in PM10) suggest that significant portion of TN was mainly composed of NHþ 4 and, to lesser extent, NO , indicating that organic nitrogen (non-water soluble) 3 is less important in the Morogoro aerosols. NH3 from biomass burning is less enriched with 15N (Turekian et al., 1998). A good correlation was obtained for both PM2.5 and PM10 between d15N and TN during sampling period (r2 0.59 and r2 0.57, pB0.05), respectively) (Fig. not shown). These correlations may suggest a presence of different forms of nitrogen and/or larger d15N ratios in aerosols. Also, a good correlation of d15N with TN may be associated with isotopic enrichment of 15N during exchange and portioning reactions of gaseous and particulate nitrogen species (e.g., NH3 and NHþ 4 ), causing a enrichment of 15 N in aerosol nitrogen (Kundu et al., 2010a; Pavuluri et al., 2010).


20

25

10

15

5

10

0

5

20

25 TN

(PM10

δ15C

8/8

7/8

6/8

5/8

3/8

2/8

1/8

29/7

28/7

5 13/6

0 12/6

10

9/6

5

7/6

15

6/6

10

5/6

20

4/6

15

1/6

δ15C (‰)

PM2.5 20

30/5

TC (μg m−3)

(b)

δ15C

15

31/5

TC (μg m−3)

TN

δ15C (‰)

(a)

9


Temporal variation of TN and d15N in (a) PM2.5 and (b) PM10 during the MayAugust 2011 sampling period at Morogoro.

3.4. Comparisons of TC, TN, and their isotopic ratios with other studies Concentrations of TC, TN, d13C and d15N in Tanzania (Tables 1 and 2) are compared with those reported from Africa and other sites around the world. Mean TC/aerosol mass ratios in Tanzania are 19.121.1% in PM2.5 and 16.1 18.1% in PM10. TC contents from our site are comparable to or lower than those (1.646.4 mg m 3) reported in tropical aerosols from the Ivory Coast in West Africa (Cachier et al., 1985) and those (14.055.0 mg m 3) from central Africa (Ruellan et al., 1999). We found higher values of d13C of TC in PM2.5 during the July and August 2011 period. Aerosol studies in the Ivory Coast and Burkina Faso (West Africa) reported larger d13C in similar months when the contribution of C4 plants sources to the atmospheric aerosols was dominant (Cachier et al., 1985). Studies from the Amazon basin in Brazil, where influence of biomass burning is significant, showed average d13C value of 25.890.5 (range: 26.9 to 24.9) in Santare´m, Para´ State, which is an area dominated with C3 plants (Martinelli et al., 2002),

and average d13C value of -24.7 (range: -26.1 to -23.5) in Rondoñia (Kundu et al., 2010b). Hence, it is likely that possible sources of organic aerosols over our sampling site could be regional biomass burning of C3 and C4 plants (Gelencse´r, 2004; Rommerskirchen et al. 2006; Vogts et al., 2009). On the other hand, the C/N ratios (6.313.9 in PM2.5 and 6.914.1 in PM10) found in Tanzania are much higher than those reported in aerosols from India and Korea (Pavuluri et al., 2010; Jung and Kawamura, 2011), whereas d15N values are comparable to those (range: 8.3 to 18.7) from the Amazon basin (mean: 11.592.1) and Piracicaba, Saõ Paulo, Brazil (mean: 10.692.8), regions that are significantly influenced by biomass (C3 and C4 plants) burning (Martinelli et al., 2002).

3.5. Contribution from burning of C3 and C4 plants to aerosol particles Biomass and biofuel combustion is common in both rural and urban areas in southern African countries including

10

Fig. 7.

S. L. MKOMA ET AL.

þ þ Relation between NO 3 -N, NH4 -N and (NH4 NO3 )-N with TN in (a) PM2.5 and (b) PM10 during the sampling period.

Tanzania. Use of wood and charcoal for domestic cooking and heating in Tanzania is enhanced in wet season (March to June), whereas field burning of agriculture residues, charcoal-making operations and forest/wild fires which cover small areas and a short duration occur in dry season (July to October) (Swap et al., 1996; Mkoma et al., 2009b). It is therefore likely that changes in d13C of TC can be modulated by biomass/biofuel burning activities including savanna fire events of southern African regions (Swap et al., 1996) and domestic wood burning. The southern African aerosol studies based on stable carbon isotopic compositions suggest a predominant burning of C3 plants (Lajtha and Marshall, 1994). Recent studies on land cover and cropland distribution reported that larger areas of East Africa where Tanzania locates are covered with C3 and C4 vegetation, which include tropical grasses, deciduous tropical forest, shrubs and woodlands

(Still et al., 2003; Rommerskirchen et al. 2006; Vogts et al. 2009). Most southern African countries are characterized by savanna ecosystems and the main vegetation types in Madagascar and Mozambique (possible source regions of air masses) are tropical forest, woodlands and shrubs (Arino et al., 2008). Land use change, especially the conversion of natural vegetation to cropland, can result in a range of environmental impacts including aerosol loading into the ambient atmosphere. Further, Cachier et al. (1985) found larger d13C values for the aerosols in Africa during dry season months. Hence, it is very likely that contributions of C4 plant burning to ambient aerosols in Tanzania are important during the sapling period. Because our sampling site is located in a typical rural area, contribution of anthropogenic TC from traffic should be minimal, whose d13C values range from 28 to 26 (Widory, 2006). The aerosol chemical mass


closure in previous study at Morogoro (Mkoma et al., 2009b) showed that elemental carbon (EC) was insignificant attributing only 1.9% of the gravimetric PM10 mass. It was mainly derived from charcoal-making process and field burning of agricultural residues (Mkoma et al., 2009b). Secondary organic aerosol formation from biogenic VOCs is assumed to be less significant than biomass/ biofuel combustion in PM2.5 (high temperature). Since our study has not been done near source site and lacks a representative emission factors for the region, we estimate relative contributions from the burning of C3 plants (%C3) and C4 plants (%C4) to TC based on stable carbon isotopic composition of TC as follows: C3 plants ð%Þ h i h i ¼ ðd13 CÞaerosol d13 C C4 = ðd13 CÞC3 d13 C C4 (5) C4 plants ð%Þ ¼ 1 ð%C3 Þ

(6)

where (d13C)aerosol is stable carbon isotopic composition of aerosol particles. (d13C)C3 and (d13C)C4 are isotope ratios of C3 and C4 plants, respectively, whose end members are assumed to be 30.5 and 13.5 based on average d13C determined for leaves of C3 and C4 vegetation (Martinelli et al., 2002). Using eqs. 5 and 6, average contributions of burning C3 plants to TC were 59% in both PM2.5 (range: 4274%) and PM10 (range: 3964%). Conversely, average contributions

11

of C4 plants were 41% in PM2.5 (range: 2658%) and PM10 (range: 3661%). The main dominant crops in the eastern and southern Africa are maize, rice, sorghum, beans and wheat, which could significantly contribute to aerosols loading during the burning season of agricultural residue in addition to wild fires. Thus, both C3 and C4 plant residues are burned and the burning products should show different isotopic composition. In our study, we found strong positive correlation between d13C of TC with nss-K (r2 0.64-0.72) and weak correlations with LG (r2 0.31-0.32) in both PM2.5 and PM10 (Fig. 8ad). These results indicate that the burning activities of C3 and C4 plants have a significant influence on organic aerosol composition (Fu et al., 2012) over Tanzania. We found active fire spots from MODIS satellite images in June to end of October (Fig. 9) in Madagascar, Mozambique and Tanzania where air masses mostly travelled through the region to our sampling site in Morogoro during our campaigns (http://earthobservatory.nasa.gov/GlobalMaps/ view.php?d1MOD14A1_M_FIRE). Our results seem to be consistent with other studies, which indicate that contributions from the burning of C3 and C4 plants are dominant in Africa (Still et al., 2003; Rommerskirchen et al. 2006; Vogts et al. 2009). However, in the large land area that is covered by savanna vegetation, contribution of biomass burning from C4 plants (e.g., grasses) to ambient aerosols could be large (Rommerskirchen

Fig. 8. Linear relation between d13C of TC with nss-K and levoglucosan in (a, b) PM2.5 and (c, d) PM10 during the sampling period in tropical aerosols from Tanzania.

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S. L. MKOMA ET AL.

reaction. We also found that NHþ 4 accounts for up to 88.7% of TN in fine aerosols.

5. Acknowledgement This study was in part supported by the Japan Society for the Promotion of Science (JSPS) through grant-in-aid No. 24221001 and the Environment Research and Technology Development Fund (B-0903) from the Ministry of the Environment, Japan. S.M. acknowledges the financial support by JSPS. We thank Mr. Filbert T. Sogomba of the Department of Physical Sciences (SUA) for sample collection and Chandra M. Pavuluri for his valuable comments. The authors also thank the NOAA Air Resources Laboratory (ARL) for the provision of the HYSPLIT transport and dispersion model and/or READY website (http://www.arl. noaa.gov/ready.php) used in this publication. Fig. 9. Biomass burning active fire spots detected by MODIS satellite images (from NASA website) over southern and eastern Africa and Madagascar in July 2011.

et al. 2006). A study in Rondoˆnia, Brazil, reported an average contribution of C4 plants of 40% (range: 4654%) (Kundu et al., 2010b). Also, Martinelli et al. (2002) reported a minimum and maximum contribution of C4 plants to aerosol particles to be 45 and 62%, respectively, with a mean of 55% in Piracicaba, southeast of the Amazon basin in Brazil. Therefore, in Tanzania depending on size fraction of the aerosol particles, the contribution of C3 and C4 plants from biomass/biofuel burning is expected to be important.

4. Summary and conclusions This study reports stable carbon and nitrogen isotopic composition of the atmospheric aerosols from Tanzania, East Africa. d13C of TC in PM2.5 ranged from 26.1 to 20.6, whereas those of PM10 showed a narrow range of 24.4 to 22.4. TC showed positive correlations with d13C and with LG (and nss-K) during the campaign, suggesting an influence of biomass burning including domestic wood burning and field burning of agricultural wastes. d13C of TC showed that average contributions of C4 plants were 41% in both PM2.5 and PM10. During dry season, d13C of fine particles are more enriched with 13 C than coarse particles, suggesting more contribution from burning of C4 plants under the dry conditions. d15N ranged from 13.422.1 (mean: 16.292.7) in PM2.5 and 10.418.7 (mean: 13.792.3) in PM10. d15N showed higher ratios in fine particles than coarse particles in both wet and dry season. The larger d15N in fine fraction suggests an isotopic enrichment of 15N in the particles during gas (NH3) and particle [(NH4)2SO4] partitioning

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